Invert emulsion fluids suitable for drilling

ABSTRACT

New drilling fluids have been invented which are invert emulsion fluids comprising an oleaginous liquid, a non-oleaginous liquid, and a protonated amine. Such fluids are acidic and thus useful in drilling wells in which acidic gases such as CO2 or H2S are likely to be encountered and break, i.e. de-emulsify, the drilling fluid.

This application claims priority from provisional patent application Ser. No. 60/023,043 filed Aug. 2, 1996.

FIELD OF THE INVENTION

This invention relates to invert emulsion fluids suitable for use in drilling wells. More particularly, the invention relates to acidic drilling fluids comprising an oleaginous liquid, a non-oleaginous liquid, an amine and an acid.

BACKGROUND OF THE INVENTION

Invert emulsion fluids, i.e. emulsions in which the non-oleaginous fluid is the dispersed phase and the oleaginous fluid is the continuous phase, are employed in drilling processes for the development of oil or gas sources, as well as, in geothermal drilling, water drilling, geoscientific drilling and mine drilling. Specifically, the invert emulsion fluids are conventionally utilized for such purposes as providing stability to the drilled hole, forming a thin filter cake, lubricating the drilling bore and downhole, and penetrating salt beds without sloughing or enlargement of the drilled hole.

Invert emulsion fluids generally consist of a three-component system, namely an oleaginous liquid such as oil which serves as a continuous phase, a non-oleaginous liquid such as water which serves as a discontinuous phase, and an emulsifying agent. The emulsifying agent serves to lower the interfacial tension of the liquids so that the non-oleaginous liquid may form a stable dispersion of fine droplets in the oleaginous liquid. A full description of such invert emulsions may be found in Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, pp. 328-332, the contents of which are hereby incorporated by reference.

Usually, lime or other alkaline materials are added to conventional invert emulsion fluids to maintain a reserve alkalinity when the invert emulsion fluid is to be used in drilling. See, for example, API Bulletin RP 13B-2, 1990, p. 22 which describes a standard test for determining excess lime in drilling mud. See also, for example, U.S. Pat. No. 5,254,531 which employs lime along with an ester oil, a fatty acid, and an amine and EP 271943 which employs lime along with oil, water, and an ethoxylated amine. In some areas acidic gases such as CO₂ or H₂ S are encountered during drilling. The acidic gases often weaken conventional invert emulsion fluids to the point of failure and render the invert emulsion fluids useless.

Thus, it would be desirable if an invert emulsion could be invented which did not fail or weaken when subjected to acidic gases such as CO₂ or H₂ S. In this manner, the invert emulsion could be employed as a drilling fluid in potentially acidic environments without apprehension of adverse affects before, during or after drilling.

SUMMARY OF THE INVENTION

A new invert emulsion fluid has been invented which comprises an oleaginous liquid, a non-oleaginous liquid, and a protonated amine having the structure R--N⁺ --H₃ wherein R represents a C₁₂ -C₂₂ alkyl group or a C₁₂ -C₂₂ alkenyl group. Such fluid is particularly useful in the drilling of wells in which CO₂, H₂ S or other acidic gases will be encountered and break or adversely affect conventional invert emulsions.

DETAILED DESCRIPTION OF THE INVENTION

As used herein, the term "invert emulsion" is an emulsion in which a non-oleaginous fluid is the dispersed phase and an oleaginous fluid is the continuous phase. The novel invert emulsion fluids of the present invention are useful in a similar manner as conventional invert emulsion fluids which includes utility in preparation for drilling, drilling, completing and working over subterranean wells such as oil and gas wells. Such methods of use of conventional inverse emulsion fluids are described in, for example, Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, the contents which are incorporated by reference, as well as, U.S. Pat. No. 5,254,531 and EP 271943 which are incorporated by reference. The advantage of the instant invert emulsion fluids is that due to the protonation of the amine it will normally not be necessary to add significant amounts of lime or another basic material to the invert emulsion fluid when an acidic substance such as CO₂ or H₂ S comes into contact with the fluid.

As used herein, the term "oleaginous liquid" means an oil which is a liquid at 25° C. and immiscible with water. Oleaginous liquids typically include substances such as diesel oil, mineral oil, synthetic oil, glycerides of fatty acids, aliphatic esters, aliphatic ethers, aliphatic acetal, dialkylcarbonates, or other such hydrocarbons.

The amount of oleaginous liquid in the invert emulsion fluid may vary depending upon the particular oleaginous fluid used, the particular non-oleaginous fluid used, and the particular application in which the invert emulsion fluid is to be employed. However, generally the amount must be sufficient to form a stable emulsion when utilized as the continuous phase. Typically, the amount of oleaginous liquid is at least about 30, preferably at least about 40, more preferably at least about 50 percent by volume of the total fluid.

As used herein, the term "non-oleaginous liquid" mean any substance which is a liquid at 25° C. and which is not an oleaginous liquid as defined above. Non-oleaginous liquids are immiscible with oleaginous liquids but capable of forming emulsions therewith. Typical non-oleaginous liquids include aqueous substances such as sea water or brine containing inorganic or organic dissolved salts, as well as, water-miscible organic compounds.

The amount of non-oleaginous liquid in the invert emulsion fluid may vary depending upon the particular non-oleaginous fluid used and the particular application in which the invert emulsion fluid is to be employed. Typically, the amount of non-oleaginous liquid is at least about 1, preferably at least about 3, more preferably at least about 5 percent by volume of the total fluid. Correspondingly, the amount should not be so great that it cannot be dispersed in the oleaginous phase. Therefore, typically the amount of non-oleaginous liquid is less than about 90, preferably less than about 80, more preferably less than about 70 percent by volume of the total fluid.

As used herein, the term "amine" refers to compounds having the structure R--NH₂ wherein R represents a C₁₂ -C₂₂ alkyl group, a C₁₂ -C₂₂ alkenyl group, a C₃ -C8 cycloalkyl group substituted with a C₉ -C₁₄ alkyl or alkenyl group, or a C₉ -C₁₄ alkyl or alkenyl group substituted with a C₃ -C₈ cycloalkyl group. Preferable R groups include straight or branched dodecyl, tridecyl, tetradecyl, pentadecyl, hexadecyl, heptadecyl, octadecyl, nodecyl, eicosyl, heneicosyl, docosyl, as well as, mixtures and unsaturated derivatives thereof. Preferable unsaturated derivatives include soyaalkylamine (Armeen S™ available from Akzo Chemicals Inc.) and tallowalkylamine (Armeen T™ available from Akzo Chemicals Inc.). Many of the other above amines are also commercially available from Akzo Chemicals Inc. under the tradename Armeen™. The aforementioned amines of the formula R--NH₂ are protonated for use in the invention. The term "protonated" means that the amine is converted to the structure R--N⁺ --H₃ X⁻. Typically, such protonation occurs due to reaction of the amine with a water-soluble acid as discussed below. Generally, the type of counter-ion, X⁻, is not particularly critical so long as it does not adversely affect the performance and characteristics of the resulting emulsion as is disclosed herein. Examples of the counter-ion include the conjugate bases of the acids described below.

The amine, when protonated, functions in the instant invention as a surfactant to lower the interfacial tension of the liquids so that the non-oleaginous liquid may form a stable dispersion of fine droplets in the oleaginous liquid. Therefore, the amount of amine should be sufficient to enable the non-oleaginous liquid to form a stable dispersion of fine droplets in the oleaginous liquid. While this amount may vary depending upon the nature and amount of the oleaginous liquid and non-oleaginous liquid, typically the amount of amine is at least about 0.1, preferably at least about 5, more preferably at least about 10 percent by weight of the total fluid. Correspondingly, the amount should not be so great that the amine interferes with the stability of the invert emulsion fluid or the performance of the invert emulsion as a drilling fluid.

As used herein, the term "acid" refers to water-soluble, i.e. at least 10 percent by volume of the acid dissolves in water, compounds which are suitable to protonate the amine and render a stable non-oleaginous fluid in oleaginous fluid emulsion. The term acid refers to both inorganic acids such as sulfuric, nitric, hydrofluoric, hydrochloric and phosphoric acid and organic acids such as citric, acetic, formic, benzoic, salicyclic, oxalic, glycolic, lactic, glutaric acid, and carbonic acid. Fatty acids such as oleic, palmitic, and stearic acid are not within the definition of acid as used herein because such acids are not water-soluble. On the other hand, water is sometimes within the definition of acid because it will protonate amines in some situations.

The amount of acid must be sufficient to protonate the amine without rendering the invert emulsion fluid so acidic that it is unstable. As one skilled in the art will appreciate, the amount of acid will necessarily vary tremendously with the strength of the acid and the particular amine to be protonated. Nevertheless, one skilled in the art having the benefit of this specification may readily determine the necessary amount of acid via routine experimentation.

The method of preparing the drilling fluids of the present invention is not particularly critical so long as an invert emulsion is formed. Generally, the components may be mixed together in any order under agitation condition. A representative method of preparing said invert emulsion fluids comprises mixing an appropriate quantity of oleaginous fluid and an appropriate quantity of amine together with continuous, mild agitation. A non-oleaginous fluid and acid is then added while mixing until an invert emulsion is formed. If weight material, such as those described below, are to be added, then the weight material is typically added after the invert emulsion fluid is formed.

One skilled in the art may readily identify whether the appropriate ingredients and amounts have been used to form an invert emulsion by using the following test:

Invert Emulsion Test

A small portion of the emulsion is placed in a beaker which contains an oleaginous fluid. If the emulsion is an invert emulsion, the small portion of the emulsion will disperse in the oleaginous fluid. Visual inspection will determine if it has so dispersed. Alternatively, the electrical stability of the invert emulsion may be tested using a typical emulsion stability tester. Generally the voltage applied across two electrodes is increased until the emulsion breaks and a surge of current flows between the two electrodes. The voltage required to break the emulsion is a common measure of the stability of such an emulsion. Other tests are described on page 166 of the book, Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C. H. Darley and George Gray, Gulf Publishing Company, 1988, the contents of which are hereby incorporated by reference.

Various surfactants and wetting agents conventionally used in invert emulsion fluids may optionally be incorporated in the fluids of this invention. Such surfactants are, for example, fatty acids, soaps of fatty acids, amido amines, polyamides, polyamines, oleate esters, imidazoline derivatives, oxidized crude tall oil, organic phosphate esters, alkyl aromatic sulfates and sulfonates, as well as, mixtures of the above. Generally, such surfactants are employed in an amount which does not interfere with the fluids of this invention being used as drilling fluids.

Viscosifying agents, for example, organophilic clays, may optionally be employed in the invert drilling fluid compositions of the present invention. Usually, other viscosifying agents, such as oil soluble polymers, polyamide resins, polycarboxylic acids and fatty acid soaps may also be employed. The amount of viscosifying agent used in the composition will necessarily vary depending upon the end use of the composition. Usually such viscosifying agents are employed in an amount which is at least about 0.1, preferably at least about 2, more preferably at least about 5 percent by weight of the total fluid. VG-69™ and VG-PLUS™ are organoclay materials and VERSA HRP™ is a polyamide resin material manufactured and distributed by M-I Drilling Fluids Company which are suitable viscosifying agents.

The invert emulsion drilling fluids of this invention may optionally contain a weight material. The quantity and nature of the weight material depends upon the desired density and viscosity of the final composition. The preferred weight materials include, but are not limited to, barite, iron oxides, calcium carbonate and the like. The weight material is typically added in order to obtain a drilling fluid density of less than 24, preferably less than 21, and most preferably less than 19.5 pounds per gallon.

Fluid loss control agents such as modified lignite, polymers, oxidized asphalt and gilsonite may also be added to the invert drilling fluids of this invention. Usually such fluid loss control agents are employed in an amount which is at least about 0.1, preferably at least about 1, more preferably at least about 5 percent by weight of the total fluid.

EXAMPLES

The following examples are submitted for the purpose of illustrating the performance characteristics of the drilling fluid compositions of this invention. These tests were conducted substantially in accordance with the procedures in API Bulletin RP 13B-2, 1990 which is incorporated herein by reference. The following abbreviations may be used in describing the results of experimentation:

"E.S." is electrical stability of the emulsion as measured by the test described in Composition and Properties of Drilling and Completion Fluids, 5th Edition, H. C. H. Darley, George R. Gray, Gulf Publishing Company, 1988, pp. 116, the contents of which are hereby incorporated by reference. Generally, the higher the number, the more stable the emulsion.

"PV" is plastic viscosity which is one variable used in the calculation of viscosity characteristics of a drilling fluid, measured in centipoise (cp) units.

"YP" is yield point which is another variable used in the calculation of viscosity characteristics of drilling fluids, measured in pounds per 100 square feet (lb/100 ft²).

"AV" is apparent viscosity which is another variable used in the calculation of viscosity characteristic of drilling fluid, measured in centipoise (cp) units.

"GELS" is a measure of the suspending characteristics, or the thixotropic properties of a drilling fluid, measured in pounds per 100 square feet (lb/100 f²).

"API F.L." is the term used for API filtrate loss in milliliters (ml).

"HTHP" is the term used for high temperature high pressure fluid loss, measured in milliliters (ml) according to API bulletin RP 13 B-2, 1990.

Example 1

In the following example invert drilling fluids are prepared utilizing amines of this invention.

Formulation 1

    ______________________________________        Materials                                                       Amount                             in Grams     ______________________________________            I.O. C.sub.16 -C.sub.18  ™ Oil (Isomerized olefin available                                125     from Amoco)     Lime                                   0     Organophilic clay (VG-PLUS ™  available from M-                                         2.0     I Drilling Fluids)     ADOGEN-151 ™  (Tall Oil Primary amine available                                      10     from Witco Chemical Company)     25% CaCl.sub.2  Brine                                                90     CaCO.sub.3                                 293     ______________________________________

The above formulation was prepared according to the following procedure: First, oil and organophilic clay were mixed in a glass jar on a Hamilton Beach mixer for 15 minutes. Then, Adogen-151™ was added and mixed for 10 minutes. Brine was then added and mixed for 15 minutes. CaCO₃ was then added and mixed for 15 minutes.

The above formulation was heat aged at 150° C. for 16 hours.

Initial and heat aged properties were measured at room temperature.

    ______________________________________                         Heat Aged                 Initial     ______________________________________                 E.S.                                     378     P.V.                                    41     Y.P.                                    40     GELS     10 sec.                                 18     10 min.                                 20     ______________________________________

5.0 grams of lime were added to the heat-aged formulation and heated at 150° F. The invert emulsion broke in 4 hours and the solids were water-wet. Electrical stability (E.S.) dropped to 6.

To the above water-wet solids formulation, 15 ml of 17.5% hydrochloric acid were added. The formulation was mixed for 10 min. The water-wet solids became oil-wet and an invert emulsion was obtained. The emulsion stability increased to 280. The following properties were measured on the acid treated formulation.

    ______________________________________                                                280             P.V.                                     50             Y.P.                                 20             GELS             10 sec.                                                    6             10 min.                                                     9     ______________________________________

5.0 g of lime were added to the acid treated formulation above and mixed for 10 min. The formulation was then heat aged at 150° F. for six hours. It was then noted that the emulsion broke and the solids became water-wet. The fluid had an electrical stability of 6.

To the above water-wet solids mixture, 10 ml of glacial acetic acid were added. The water-wet solids became oil-wet again. The electrical stability increased to 295.

The above example shows that the protonation of the amine makes the invert emulsion and upon deprotonation, the emulsion is broken.

Example 2

The following formulation was prepared to demonstrate the utility of amine surfactant of this invention in 50/50 oil to water ratio oil base mud.

Formulation 2

    ______________________________________       Materials      Amount in Grams     ______________________________________           I.O. C.sub.16 -C.sub.18  ™                    121     VG-PLUS ™                                     2.0     ADOGEN-151 ™                    12.0     25% CaCl.sub.2                                 200     CaCO.sub.3     ______________________________________                    61

The above formulation was prepared in a manner similar to Example 1 and heat aged at 150° F. for 16 hours. The following initial and heat-aged properties were measured.

    ______________________________________                         Heat Aged                 Initial     ______________________________________                 E.S.                                     150     P.V.                   37    34     Y.P.                                    43     GELS     10 sec                                  20     10 min                                  22     ______________________________________

5.0 g lime was then added to the above formulation and it was heat-aged to 150° F. for 4 hours. The solids became water-wet. The electrical stability was 6.

15.0 ml. of 17.5% hydrochloric acid were then added to the water-wet formulation above and mixed for 10 min. The water-wet solids became oil-wet. The electrical stability increased to 208. The mud was oil dispersible.

The above example shows that the protonation of amine-surfactant of this invention makes stable water-in-oil emulsions.

Example 3

The following formulation was prepared in a manner similar to Example 1 to demonstrate the use of amine surfactant in protonated form to make stable water-in-oil emulsions.

Formulation 3

    ______________________________________     Materials                Amount in Grams     ______________________________________                I.O. C.sub.16 -C.sub.18  ™                             12.1     VG-PLUS ™                                                2.0     JET-AMINE-PS ™ (primary soya available from                             12.0     Jetco Chemical)     17.5% HCl               10.0     25% CaCl.sub.3 Brine    190     CaCO.sub.3              61     ______________________________________

The above formulation was heat-aged at 150° F. for 16 hours. The following properties were measured after heat-aging.

    ______________________________________                                              216             P.V.                                      39             Y.P.                                      51             GELS             10 sec                                                      22             10 min                                                      23     ______________________________________

10 g of lime were mixed with the above formulation and the resulting formulation was heat-aged at 150° F. for 5 hours. The emulsion was converted to an oil-in-water emulsion with electrical stability of 10. The following properties were measured on this oil-in-water emulsion

    ______________________________________                                              10             P.V.                                       20             Y.P.                                       18                       GELS             10 sec                   6             10 min                                                13     ______________________________________

15 ml of 17.5% hydrochloric acid was then mixed with the above formulation and it was converted to an oil-base mud with electrical stability 153.

The above example establishes that the amine emulsifier in protonated form of this invention forms a water-in-oil emulsion. Upon deprotonating with lime, it forms an oil-in-water emulsion.

Example 4

The following formulations, Formulations 4, Formulation 5 and Formulation 6, were prepared in a manner similar to Example 1 to demonstrate the use of synthetic oils in preparing invert emulsions of this invention.

Formulation 4

    ______________________________________                          Formulation 5    Formulation 4                                         Formulation 6     Materials                        Amount in Grams                              Amount in Grams                                          Amount in Grams     ______________________________________     SARAPAR ™            121       121         21            147 (oil avail-            able from Shell            Oil)            VG-PLUS ™                      2.0         2.0 2.0            Emulsifiers                      JET-AMINE P.T. ™                                      JET-AMINE P.S. ™                                  ADOGEN-151 ™                                (Primary Tallow                                     (Primary Soya       (Tall Oil Primary                               amine available                                  amine available    amine)                                 form Jetco                                     from Jetco        12.0                                  Chemical)                                      Chemical)                                            12.0            17.5% HCl            10                                                   10                10            25% CaCl.sub.2                                200                                                  200               200            Barite                                 66     ______________________________________                                  66

The following initial properties were measured on the above formulations.

    ______________________________________     Formulation 4      Formulation 5                                  Formulation 6     ______________________________________     E.S.     159         160          125     P.V.                                           24     Y.P.                 73                                                    14     GELS                                                    7                                                    8     ______________________________________

The above formulations were then heat-aged at 150° F. for 16 hours. The following properties were then measured at room temperature.

    ______________________________________     Formulation 4      Formulation 5                                  Formulation 6     ______________________________________     E.S.    258            188         105     P.V.                 29                                                     21     Y.P.                 36                                                     15     GELS                                                     7                                                     9     ______________________________________

10 grams of lime were added to each of the above heat aged Formulations 4-6. The solids became water-wet. Electrical stability dropped to 25, 22 and 10 respectively. The water-in-oil emulsions were broken.

Glacial acetic acid was then added to each of the above water-wet solids mix to neutralize the lime and protonate the amine surfactant. Upon protonating the amine surfactant, the formulations became water-in-oil invert emulsions. Electrical stability increased to 121, 138 and 110, respectively.

The above example demonstrates the use of amine surfactant in protonated form to make the invert emulsion of this invention.

While the compositions and methods of this invention have been described in terms of preferred embodiments, it will be apparent to those of skill in the art that variations may be applied to the processes and compositions described herein without departing from the concept, spirit and scope of the invention. All such similar substitutes and modifications apparent to those skilled in the art are deemed to be within the spirit, scope and concept of the invention as set out in the following claims. 

What is claimed is:
 1. A method for reversibly converting an invert emulsion drilling fluid into a regular emulsion drilling fluid, the method comprising admixing a base with the invert emulsion drilling fluid, wherein the invert emulsion drilling fluid comprises:1) an oleaginous liquid; 2) a non-oleaginous liquid; and 3) a protonated amine having the structure

    R--N.sup.+ --H.sub.3 B.sup.-

wherein R is a C₁₂ -C₂₂ alkyl group or a C₁₂ -C₂₂ alkenyl group, and B⁻ is the conjugate base of a water soluble acid, said invert emulsion being substantially free of an alkali reserve; and the base is functionally able to deprotonate the amine surfactant, in sufficient quantities so as to convert the invert emulsion to an oil-in-water type emulsion.
 2. A method for reclaiming an invert emulsion after use as a drilling, completion or workover fluid in subterranean wells containing an acidic gas, the method comprising(a) admixing the fluid with a base, wherein the fluid comprises:1) an oleaginous liquid; 2) a non-oleaginous liquid; and 3) a protonated amine having the structure

    R--N.sup.+ --H.sub.3 B.sup.-

wherein R is a C₁₂ -C₂₂ alkyl group or a C₁₂ -C₂₂ alkenyl group, and B⁻ is the conjugate base of a water soluble acid, said invert emulsion being substantially free of an alkali reserve; and the base being functionally able to deprotonate the protonated amine surfactant, in sufficient quantities so as to convert the invert emulsion to an oil-in-water type emulsion; (b) separating solids from oil-in-water type emulsion; and (c) admixing the oil-in-water type emulsion with an acid, the acid being functionally able to protonate the amine surfactant, in sufficient quantities so as to convert the oil-in-water type emulsion to a water-in-oil type emulsion.
 3. A method of drilling a subterranean well in the presence of acidic gases, the method comprisingdrilling said subterranean well with an invent emulsion drilling fluid, the drilling fluid includingi) an oleaginous fluid; ii) a non-oleaginous fluid; and iii) a protonated amine surfactant having the formula

    .sup.+ B.sup.-

wherein R is a C₁₂ -C₂₂ alkyl group or a C₁₂ -C₂₂ alkenyl group, and B⁻ is the conjugate base of a water soluble acid; and wherein the invert emulsion drilling fluid is substantially free of an alkali reserve; and wherein the addition of sufficient base to deprotonate the protonated amine surfactant reversibly converts the invert emulsion into a regular emulsion.
 4. A method of reversibly converting a drilling fluid from an invert emulsion into a regular emulsion, the method comprisingadding a base to the invert emulsion, wherein the invert emulsion comprises:an oleaginous fluid; a non-oleaginous fluid; and a protonated amine surfactant having the formula

    .sup.+ B.sup.-

wherein R is a C₁₂ -C₂₂ alkyl group or a C₁₂ -C₂₂ alkenyl group, and B⁻ is the conjugate base of a water soluble acid; and wherein the invert emulsion drilling fluid is substantially free of an alkali reserve and wherein the base is functionally able to deprotonate the protonated amine surfactant and the base is in a sufficient amount so as to convert the invert emulsion into a regular emulsion.
 5. The method of claim 4 further comprising:adding an acid to the regular emulsion, wherein the acid is functionally able to protonate the deprotonated amine surfactant and the acid is in a sufficient amount so as to convert the regular emulsion into an invert emulsion. 